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The origin of enhanced O2+ production from photoionized CO2 clusters

Ganguly, Smita LU ; Barreiro, Darío ; Walsh, Noelle LU ; Oostenrijk, Bart LU ; Sorensen, Stacey L LU orcid ; Díaz-Tendero, Sergio and Gisselbrecht, Mathieu LU orcid (2022) In Communications Chemistry
Abstract
CO2-rich planetary atmospheres are continuously exposed to ionising radiation driving major photochemical processes. In the Martian atmosphere, CO2 clusters are predicted to exist at high altitudes motivating a deeper understanding of their photochemistry. In this joint experimental-theoretical study, we investigate the photoreactions of CO2 clusters (≤2 nm) induced by soft X-ray ionisation. We observe dramatically enhanced production of O2- from photoionized CO2 clusters compared to the case of the isolated molecule and identify two relevant reactions. Using quantum chemistry calculations and multi-coincidence mass spectrometry, we pinpoint the origin of this enhancement: A size-dependent structural transition of the clusters from a... (More)
CO2-rich planetary atmospheres are continuously exposed to ionising radiation driving major photochemical processes. In the Martian atmosphere, CO2 clusters are predicted to exist at high altitudes motivating a deeper understanding of their photochemistry. In this joint experimental-theoretical study, we investigate the photoreactions of CO2 clusters (≤2 nm) induced by soft X-ray ionisation. We observe dramatically enhanced production of O2- from photoionized CO2 clusters compared to the case of the isolated molecule and identify two relevant reactions. Using quantum chemistry calculations and multi-coincidence mass spectrometry, we pinpoint the origin of this enhancement: A size-dependent structural transition of the clusters from a covalently bonded arrangement to a weakly bonded polyhedral geometry that activates an exothermic reaction producing O+2. Our results unambiguously demonstrate that the photochemistry of small clusters/particles will likely have a strong influence on the ion balance in atmospheres. (Less)
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author
; ; ; ; ; and
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Communications Chemistry
publisher
Springer Nature
external identifiers
  • scopus:85124393595
ISSN
2399-3669
project
Studying photodissociation of core ionised CO2 clusters using ion-momentum imaging
language
English
LU publication?
yes
id
6777890a-9b2d-4714-9fc0-14d81acb3ca2
alternative location
https://www.nature.com/articles/s42004-022-00629-z
date added to LUP
2022-02-05 00:39:44
date last changed
2024-06-13 16:47:33
@article{6777890a-9b2d-4714-9fc0-14d81acb3ca2,
  abstract     = {{CO2-rich planetary atmospheres are continuously exposed to ionising radiation driving major photochemical processes. In the Martian atmosphere, CO2 clusters are predicted to exist at high altitudes motivating a deeper understanding of their photochemistry. In this joint experimental-theoretical study, we investigate the photoreactions of CO2 clusters (≤2 nm) induced by soft X-ray ionisation. We observe dramatically enhanced production of O2- from photoionized CO2 clusters compared to the case of the isolated molecule and identify two relevant reactions. Using quantum chemistry calculations and multi-coincidence mass spectrometry, we pinpoint the origin of this enhancement: A size-dependent structural transition of the clusters from a covalently bonded arrangement to a weakly bonded polyhedral geometry that activates an exothermic reaction producing O+2. Our results unambiguously demonstrate that the photochemistry of small clusters/particles will likely have a strong influence on the ion balance in atmospheres.}},
  author       = {{Ganguly, Smita and Barreiro, Darío and Walsh, Noelle and Oostenrijk, Bart and Sorensen, Stacey L and Díaz-Tendero, Sergio and Gisselbrecht, Mathieu}},
  issn         = {{2399-3669}},
  language     = {{eng}},
  month        = {{02}},
  publisher    = {{Springer Nature}},
  series       = {{Communications Chemistry}},
  title        = {{The origin of enhanced O2+ production from photoionized CO2 clusters}},
  url          = {{https://www.nature.com/articles/s42004-022-00629-z}},
  year         = {{2022}},
}